Solubilized derivatives of rosins



3,041,171 SOLUBKLIZED DERIVATIVES F ROSINS Charles V. Wilson and William J. Knox, Jr., Rochester,

N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Apr. 30, 1959, Ser. No. 809,911

16 Claims. (Cl. 96-94) This invention relates to new compositions of matter obtained from commercial rosin and to the use of these products, more particularly, their use as detergents and as coating aids.

Rosin is a relatively inexpensive, commercially available material widely used for various purposes, as such, and in several modifications, for example those produced by hydrogenation or dehydrogenation. Rosin acids are useful surface-active agents particularly in combination with fatty soaps to impart increased solubility and foaming power. However, rosin soaps tend to discolor on aging, like the fatty acid soaps, they are not resistant to lime and acids.

In order to avoid discoloration, rosin is modified commercially by hydrogenation or dehydrogenation. The former process eliminates the double bonds, while the latter partially aromatizes the compounds. In either case, the resulting products are less suspectible to oxidative deterioration. These hydrogenated or dehydrogenated rosins are used to increase the eiliciency of soaps both for laundry and toilet purposes.

These treatments, however, do not make the materials lime resistant nor do they increase the solubility substantially. One of the components of rosin, laevopimaric acid is made more soluble by reacting with maleic anhydride and hydrolysing the maleopimaric acid thus formed to the sodium salt. However, laevopimaric acid makes up only to of the rosin, and it has been considered desirable to solubilize all the rosin acids in the mixture. We have found that the solubility of these complex molecules may be improved and that in several cases the products have a high degree of calcium tolerance.

We have also found that many of these materials have detergent properties which permit their use as wetting agents and coating aids. 7

There are many instances in industry where it is desirable to apply one or more relatively thin coatings or layers to various type bases. In the photographic industry particularly, products are prepared by applying relatively thin coatings to various types of bases such as film and paper bases. It is usually preferable that these coatings be uniform and that the coated base be free of bare spots or other imperfections. It is also desirable to apply such coatings at good production speeds for efiiciency of operation. I

In the coating of photographic film or paper with a gelatin layer such as a photographic emulsion or other coating compositions, a uniform coating must be obtained. In the absence of a coating aid, numerous small crescent-shaped uncoated areas are observed in the final product. These defects may be the size of a pin head with streaks running from the points of the crescent in a direction opposite to that of coating. Sometimes lightly coated areas from 5 to 10 in diameter may also appear.

Various surface-active agents have been employed in gelatin coating compositions for facilitating coating pro- 3,041,171 Patented June 26, 1952 cedures or operations. For instance, saponin has been used for this purpose and eliminates many of the defects in coatings, giving a uniformly even coating particularly where the gelatin layer is applied to a dry surface.

Saponin, however, is a naturally occurring material of vegetable origin and may vary markedly from batch to batch in quality as well as composition. The quality of some batches of saponin may cause an increase in fog or a decrease of sensitivity of certain emulsions or may even result in no improvement in the coating properties of the composition to which it is added. These wide variations in the quality of this natural material make preferable, as coating aids, surface-active agents which are reproducible from batch to batch both in chemical composition and coating behavior.

A number of synthetic agents have utility for coating purposes, but they are often deficient in some respects. For example, certain coating aids naturally contribute to the ease of coating, but they are not useful because of adverse photographic properties. Various other difliculties and problems arise in the photographic industry in the application of gelatin layers to a support.

One object of this invention is to solubilize complex molecules such as rosin, rosin acids, and the like. Another object of this invention is to provide highly watersoluble rosin derivatives which have a high degree of calcium tolerance. An additional object is to provide a coating aid free from photographic activity for coating photographic emulsions. Another object is to provide a method for applying gelatin coatings in the preparation of photographic materials which are uniformly even and repellency free and which are photographically inert. A further object of our invention is to prepare wetting agents which may be used as detergents. Other objects will appear herein.

We have found that ordinary rosin, laevopimaric acid, the mixture of rosin acids remaining after removal of the laevopimaric acid, and related products will react with isocyanato esters, particularly those derived from aspartic and glutamic acids. The resulting materials can be selectively hydrolyzed to the sodium salts of acids which are highly water soluble and have a high degree of calcium tolerance. The reaction'with the abietic acid portion of the mixture (and the other react similarly) may be represented as follows: H30 0 0 OH E10 OCNOHCOOR (ormnooon (CH2) n0 0 0 R H 0 0 ONHCHC 0 0 R EtRH C 02 mo omens), NaOH H O OONHCHCOONa (CHB)2 CH-COONa C w ah in which R may be H, CH C H -CH(CH C H or -(CH COONa where n=1 to 3. These products are hereinafter referred to as sodium salts of maleopimaroylamino acids. Thus, for example, if R is CH the product is trisodiu-rn maleopimaroylglycinate, while if R is -CH CO ONa, the product is tetrasodium maleopimaroylaspartate.

Other products derived from rosin, for example, Abitol and Rosin Amine D and various hydrogenated and dehydrogenated forms of the mixture of alcohols or amines, as well as their polyoxyethylene derivatives also react with isocyanato esters to produce urethanes and ureas respectively.

Rosin Amine D is the trade name for a commercially available material which is essentially l-aminomethyl-7- isopropyl 1,4a dirnethyl 1,2,3,4,4a,9,10,10a-octahydrophenanthrene.

Abitol and the products derived from it by treatment with ethylene oxide are particularly useful because further treatment with any of a number of isocyanato esters produces, after selective hydrolysis, products of high water solubility and a high degree of calcium tolerance. Substances of this type are available on the market under the trade names synthetics AD-SO, synthetics AD-lSO and Synthetics AD-400. A-bitol comprises a mixture of the three alcohols having the following structures:

CH CHaOH C (C a)2 The derivatives of Abitol formed by treatment with ethylene oxide may be represented as a mixture of the following three structures:

W CH(CHB)I 01103113) CH3 CHzO (CHaCHzO) nH n rray be 1-10 but in our preferred embodiment, n is 3 to The materials described in the following examples as sodium rosinyl glutamate and sodium rosinyl aspartate are amides which were obtained by reacting a mixture of rosin acids with dirnethyl isocyanatoglutarate or succinate. The term rosiny is used here to signify the acyl radicals of the mixture of resin acids present in commercial rosin. Tetra-sodium maleopimaroylglutamate and asparate are also amides prepared by reacting maleopimaric acid with the appropriate isocyanato ester and selectively hydrolyzing the primarily formed amide-ester. The Rosin Amine D derivative referred to in Example 12 is a urea prepared by reacting Rosin Amine D with the isocyanato ester. The last three materials in Examples 13-16 are urethanes obtained by the reaction of the isocyanato ester with a rosin alcohol known as-Abitol or polyethoxy derivative thereof.

To prepare gelatino coating compositions, 0.13-1.0 gram of the water-soluble rosin derivative is used per pound of gelatin.

The following examples illustrate our invention but are not to be construed as limiting it in any way.

Example 1.-Sodium Rosinylaspartate A mixture of 60 parts of a commercial rosin, 39 parts (somewhat less than one molar equivalent based on abietic acid) of diethyl isocyanatosuccinate, and 50 parts of dry chlorobenzene was heated for 16-18 hours near the boiling point of the solvent (BO- There was evolution of carbon dioxide during the first few hours of the reaction. The solvent was removed under reduced pressure, and the residue (95 parts) dissolved in 400 parts of alcohol and filtered. To the alcohol solution at 33 was added a solution of 15 parts of sodium hydroxide in 15 parts of water 75 and parts of alcohol. Precipitation of a solid began shortly after mixing, and the temperature rose to about 45. The solid tends to form a gum if heated above this temperature so the mixture was allowed to stand for several hours to insure complete hydrolysis of the ester groups. The resulting sodium salt was collected on a filter, washed with acetone, and dried. The yield was about 30 parts.

Removal of solvent from the filtrate, using benzene to azeotrope olf the last of the water, left 52 parts of a darker solid thanthat described above.

Both solids are very soluble in water, have a high calcium tolerance, and are active surface-active agents.

Since commercial rosin is a mixture of several related acids, the reaction is best represented as follows:

Rosin Rosin-C ONHOHC O OCzHu CHzC 0 0 Q2115 Example 2.--Tetras0dium Maleopimoi'oylaspartare A solution of 40 grams (0.1 m.) of maleopimaric acid (obtained from gum oleoresin by treatment with maleic anhydride as described in U.S. Patent 2,359,980) and 21.5 g. (0.1 m.) of diethylisocyanato succinate in 60 ml. of chlorobenzene was heated for 16-18 hours at the boiling point. Carbon dioxide was evolved during the early stages of the reaction. The solvent was removed by heating on the steam bath under reduced pressure, and the residue was dissolved in 300 ml. of alcohol. Treatment of this solution with a solution of 16 g. (0.4 m.) of sodium hydroxide in aqueous alcohol (made by dissolving the sodium hydroxide in 20 ml. of water and diluting with 200 ml. of alcohol) caused precipitation of a gummy solid. The mixture was heated for an hour at 65, allowed to come to room temperature, and the aqueous alcohol removed by decantation. Acetone was added and the solid ground to a powder by use of a mortar and pestel, or alternately, by vigorous stirring with a Lightnin mixer. The solid was collected on a filter, washed with acetone and dried. The yield'of product was 55-60 g. It had high water solubility, excellent calcium tolerance, and good surface-active properties.

A similar product, tetrasodium maleopimaroylglutamate, results by treatment of maleopimarie acid with dimethyl isocyanatoglutarate by the same procedure.

Similar products may be obtained by using isocyanato esters such as those derived from glycine, tat-alanine, leucine and the like.

Example 3.-Urea From Rosin Amine D (Hercules) and Dimethyl Isocyanato Succinate Dimethyl isocyanato succinate (23.5 g.) was added to 36 g. (1 molar equivalent) of Rosin Amine D. There was considerable heat of reaction, the temperature rising to 7080. The mixture was heated for several hours at 90-100". On cooling it set to a resin-like mass. It was dissolved in alcohol and treated with g. of sodium hydroxide dissolved in 12 ml. of water, and diluted with alcohol. There was a small temperature rise; hydrolysis was completed by heating for 1-2 hours at 65. The sodium salt which separates in resinous form became solid on cooling. The aqueous alcohol was removed by decantation, and a mixture of acetone and ethyl acetate added. After standing overnight, the solid was broken up, collected on a filter, washed with acetone, dried, powdered, slurried with acetone, refiltered, and dried. The product (52 g.) was soluble in water but not tolerant of calcium. It was essentially N-a,B-dicarboXyethyl-N-3- isopropyl 7,10a dimethyl 5,6,6a,7,8,9,10,l0a octahydrophenanthrylurea (disodium salt).

Example 4.-Sodium N-Carbo Abityl Oxyglafamate was dissolved in 1500 ml. of ethanol and treated while being stirred with g. of sodium hydroxide in ml.

of water. After the addition of the alkali, the mixture was heated at 75 for an hour, cooled, and the solid collected on a filter, Washed with alcohol, and dried. There 7 was obtained about 750 g. of granular product which has high solubility and good calcium tolerance. The material was an excellent surface-active agent and a good coating assistant.

Example 5.-N-Carb0 Abityl Oxypolyethoxyglycine (Na Salt) 7080 for 5-6 hours, and the product dissolved in 300 ml. of alcohol. To the alcoholic solution Was added 10 g. of sodium hydroxide in 12 ml. of Water. The mixture was heated at 65-70 for about one-half hour and then allowed to stand for several hours. A small amount of solid that separated the solution was removed by filtration; it was the di-substituted urea formed from the ethyl isocyanatoacetate. The water and alcohol were removed from the filtrate under reduced pressure to give 88 g. of a syrup which could be dissolved in water to give a solution of any desired strength. Alternately, the hydrolysis can be carried out with water and the aqueous solution thus formed adjusted to the desired strength. Sodium N-carboabityloxypolyethoxyglutamate can be prepared by a similar procedure.

' Example 6 In an air knife application to paper of a silver bromide emulsion involving the use of sodium rosinyl glutamate Concentra- Repellen- Photographic Coating Aid tion grams cies per Properties per pound 7.5 it. sq.

0. 0 1 Satisfactory.

Example ,7

In an experiment similar to that described in Exam- Abito1 is essentially a mixture of three alcohols of the following structures:

' .l he name given to the product of this example is chosen to indicate that said product is a. mixture of the urethanes of these three alcohols.

ple 6, but involving sodium rosiny aspartate (SRA), the following results were obtained:

Coneentra- Repcllen- Photographic Coating Aid tion grams cies per Properties per pound 7.5 it. sq.

0. 3 Satisfactory.

- 0.5 0 Do. 1. 0 2 D0.

Example 8 In an experiment similar to that described in Example 6, but involving tetra-sodium maleopimaroylglutamate (SMG) as a coating aid, the following results were obtained:

Conoentra- Rcpellen- Photographic Coating Aid tlon grams cies per Properties per pound 7.5 ft. sq.

0. 0 6 Satisfactory. 0. l3 1 D0. 0.25 0 Do. 0.5 0 Do. 1.0 0 Do.

Example 9 In an experiment similar to that described in Example 6, but involving tetra-sodium maleopimaroylaspartate (SMA) as a coating aid, the following results were obtained:

Concentra- Rcpellen- Photographic Coating Aid tion grams cies per Properties per pound 7.5 ft. sq.

0.0 3 Satisfactory.

0. l3 0 Do.

Example 10 In an experiment similar to that described in Example 6, but involving the Rosin Amine D Derivative (RDA) as a coating aid, the following results were obtained:

Concentra- Repellen- Photographic Coating Aid tion grams cics per Properties per pound 7.5 ft. sq.

0. 0 3 Satisfactory.

Example 11 In an experiment similar to that described in Example 6, but involving the product of Example 4, sodium N-carboabityloxyglutamate (SCG), as a coating aid, the following results were obtained:

' Concentra- Repellen- Photographic Coating Aid tion grams cies per Properties per pound 7.5 ft. sq.

0.0 Satisfactory. 0.13 10 Do. 0.25 2 D0. 0.5 0 Do. 1.0 0 D0.

Example 12 In an experiment similar to that described in Example 6, but involving sodium N-carboabity1oxyglyc1nate 8 (SAG), as a coating aid, the following results were obtained:

Concentra- Repellen- Photographic Coating Aid tion grams cies per Properties per pound 7.5 ft. sq.

0. 0 6 Satisfactory.

Example 13 In ple 6, but involving a product as described in Example 5, sodium N-carboabityloxypolyethoxy glutamate (SCPG), the following results were obtained:

an experiment similar to, that described in Exam- Concentra- Repellen- Photographic Coating Aid tion grams cies per Properties per pound 7.5 ft. sq.

0.0 7 Satisfactory. 0.13 8 Do. 0.25 0 Do. 0.5 1 Do. 1.0 0 Do.

Example 14 In an experimental pelloid coating obtained by using the slide hopper coating technique described in US. Patout No. 2,681,294 and involving the product of Example 4, sodium N-carboabityloxyglutamate (SCG), at 0.22 gm./lb. of coating melt as a coating aid, the following results were obtained:

Repel- Streak- Nature of lencies Mottle iness Dried 25 ft. sq. Surface Blank .4 S1 to sl+ s1 Rough. SCG 0 s1 Do.

Example 15 In an experiment similar to that described in Example 14, but involving the product of Example 5, sodium N-carboabitylpolyethoxyglycinate (SAPG), as a coating aid, the following results were obtained:

Repel- Streak- Nature of lencies Mottle iness Dried 25 ft. sq. Surface Blank 10 Med sl Rough. SAPG 2 s1 sl Do.

Example 16 In an experiment similar to that described in Example 14, but involving the product mentioned in Example 5, sodium N-carboabityloxypolyethoxyglutamate (SCPG), the following results were obtained:

Repel- Streak- Nature of lencies Mottle iness Dried 25ft. sq. Surface Blank 13 sl sl SCPG 2 Si sl Example 18 In runs similar to those in Example 17 but using the product of Example 5, sodium N-carboabityloxypolyethoxy glycinate, at concentrations of 1.0 gram to 2.5 pounds of wet emulsion and 1 gram to 7.7 pounds of overcoat melt, comparably good results were obtained.

Examples 17 and 18 are wet-on-wct coating examples where a warm overcoat is applied to a wet emulsion surface which has been set by chilling.

Example 19.Malepimaroyl Chloride Thionyl chloride (238 g., 2 moles) was added to 200 g. (0.5 mole) of maleopimaric acid and the mixture allowed to stand for 24 hours. It was then heated at 60 for one hour. The excess thionyl chloride was removed by distillation, first under atmospheric pressure, and finally with the aid of a water pump. The resulting dark colored solid was treated with 125 ml. of acetone and broken up into a granular product. Low boiling petroleum ether (100 ml.) was added and the mixture chilled to C. The product Was collected on a filter, washed with 100 ml. of petroleum ether and dried. The yield of crude material was 174 g. (83 percent). A sample, recrystallized from benzene-ether melted at 184 186 C. The literature [Graff, J. Am. Chem. Soc., 68, 1937 (1946)] records 165.

Anal.-Calc. for C H O Cl: C, 68.9; H, 7.4; Cl, 8.4. Found: C, 68.6; H, 7.2; G1, 8.5.

Example 20.S0dium Maleopimaroylglutamate Monosodium glutamate (169 g., 1 mole) was dissolved in a solution of 40 g'. (1 mole) of sodium hydroxide in 400 ml. of water and 150 ml. of acetone. The solution was heated to 45-50" C., and while stirring, 418- g. (1 mole) of maleopimaroyl chloride and 120 g. (3 moles) of sodium hydroxide dissolved in one liter of water were added simultaneously over an hour period. The acid chloride was added in 25-gram portions at 4-minute intervals, and the alkali at such a rate that the solution remained alkaline. Stirring was continued at 50-55 for 1-2 hours after the addition was complete. The solution was then heated and stirred in the steam bath until the temperature reached 92; this served to remove the acetone. Water was added to produce a solution containing an estimated 25 percent total solids, including approximately 2 percent sodium chloride. This aqueous solution was equivalent in its coating properties to the product obtainedby the isocyanate procedure.

The term rosiny has been applied to the 19 carbon alkylated hydrophenanthrene nucleous which occurs in the rosin acids and the partially hydrogenated rosin acids. Rosinyl" is thus well known as the generic name of the C H and C H radicals which occur in abietic acid, levopimaric acid, neoabietic acid, dextropimaric acid and like acids whose general formula is and dihydroabietic acid, dihydrolevopimaric acid, dihydrodextropimaric acid and like acids whose general formula is C H COOH. The term rosiny is likewise here applied broadly to the C H and the C H radicals which occur in the rosin acids and the diihydrorosin acids. The term hydrorosinyl refers to the C H radical having the ring structure of the fully hydrogenated rosin acids, and the term dehydrorosinyl refers to the C H radical having the ring structure of dehydroabietic acid. The terms norabietyl, nordihydroabietyl, nortetrahydroabietyl, and nordehydroabietyl are the specigc names applied to those radicals which have the ring structure of abietic acid, dihydroabietic acid, tetrahydroabietic acid and dehydroabietic acid respectively wherein the point of linkage is carbon number one.

When the compositions disclosed herein are used as coating aids, the aid may be incorported in a gelatin coating which is coated on various supports such as paper, film base, glass and the like. In addition, some of these materials may be used for coatings over wet surfaces as well as dry surfaces. For instance, they may be used as coating aids when a gelatin emulsion is coated over a previous gelatin emulsion which is still in a wet condition suchas a wet chilled emulsion surface. Moreover, some of these coating aids may be used in a series of gelatin layers and the subsequent gelatin layer containing one of these coating aids may be coated over a wet chilled emulsion surface, in which wet chilled emulsion has been incorporated one of these coating aids. Other combinations of layers in wet or dry condition and in various sequences in which one or more layers contain one of these coating aids are intended to be within the scope of our invention.

Water-soluble salts other than the sodium salts are also within the scope of this invention and may he formed by using the appropriate hydroxide such as potassium hydroxide, ammonium hydroxide and the like to hydrolyze the ester.

These coating aids are also advantageous with a multiple layer coating technique of the type described in U.S. patent application Serial No. 489,863 filed August 15, 1955.

This application is a continuation-in-part of U.S. patent application Serial No. 603,195 filed August 9, 1956.

We claim:

1. A coating composition comprising an aqueous solution of gelatin containing therein as a coating aid 0.13- 1.() gram of water-soluble sodium rosinyl glutamate per pound of gelatin.

2. A coating composition comprising an aqueous solution of gelatin containing therein as a coating aid 0.13- 1.0 gram of Water-soluble sodium rosinyl aspartate per pound of gelatin.

3. A coating composition comprising an aqeous solution of gelatin containing therein as a coating aid 0.13- 1.0 gram of water-soluble tetrasodium maleopimaroylglutamate per pound of gelatin.

4. A coating composition comprising an aqueous solution of gelatin containing therein as a coating aid 0.13- 1.0 gram of Water-soluble tetrasodium maleopimaroylasparate per pound of gelatin.

5. A coating composition comprising an aqueous solution of gelatin containing therein as a coating aid 0.13- 1.0 gram per pound of gelatin of a mixture of watersoluble salts having the following structures:

CH3 CHzOCONHCHGOONa CHZCHZCOONS.

CEa/CHQOCONHCIEHCOONQ.

q CHgCHzOOONE CH 7 CHa/CHzOOONHOHCOONa CH2CH2COONB so that the structures are represented in the mixture in a ratio of 45:15:40 respectively.

6. A coating composition comprising an aqueous solution of gelatin containing therein as a coating aid 0.13- 1.0 gram per pound of gelatin of a water-soluble salt prepared by reacting an isocyanato ester having the following general formula:

OCNCHCOOR in which R is an alkyl grouphaving l-3 carbon atoms and R is selected from the class consisting of H, -CH CO0R, -CH CH COOR, and

-CH CH COOR ethoxyglutamate per pound of gelatin.

8. A coating composition comprising an aqueous solution of gelatin containing therein as a coating aid 0.13- 1.0 gram of water-soluble sodium N-carboabityoxypolyethoxyglycinate per pound of gelatin.

9. A coating composition as described in claim 1 in which the aqueous solution of gelatin is a photographic gelatino-silver halide emulsion.

10. A coating composition as described in claim 2 in which the aqueous solution of gelatin is a photographic I .gelatino-silver halide emulsion.

11. A coating composition as described in claim 3 in which the aqueous solution of gelatin is a photographic gelatino-silver halide emulsion.

12. A coating composition as described in claim 4 in which the aqueous solution of gelatin is a photographic gelatino-silver halide emulsion.

13. A coating composition as described in claim 5 in which the aqueous solution of gelatin is a photographic gelatino-silver halide emulsion.

14. A coating composition as described in claim 6 in which the aqueous solution of gelatin is a photographic gelatino-silver halide emulsion.

15. A coating composition as described in claim 7 in which the aqueous solution of gelatin is a photographic gelatino-silver halide emulsion.

16. A coating composition as described in claim 8 in which the aqueous solution of gelatin is a photographic gelatino-silver halide emulsion.

References Cited in the tile of this patent UNITED STATES PATENTS 2,354,662 Bryce Aug. 1, 1944 2,376,687 Goldstein et a1 May 22, 1945 2,684,300 Wilson et a1. July 20, 1954 2,698,250 Leichner Dec. 28, 1954 2,771,464 Hastings et a1. Nov. 20, 1956 FOREIGN PATENTS 676,511 Germany June 8, 1939 OTHER REFERENCES Dreshfield et al.: Paper Trade Journal, July 17, 1941, pages 34-36. 

6. A COATING COMPOSITION COMPRISING AN AQUEOUS SOLUTION OF GELATIN CONTAINING THEREIN AS A COATING AID 0.131.0 GRAM PER POUND OF GELATIN OF A WATER-SOLUBLE SALT PREPARED BY REACTING AN ISOCYANATO ESTER HAVING THE FOLLOWING GENERAL FORMULA:
 14. A COATING COMPOSITION AS DESCRIBED IN CLAIM 6 IN WHICH THE AQUEOUS SOLUTION OF GELATIN IS A PHOTOGRAPHIC GELATINO-SILVER HALIDE EMULSION. 